U.S. patent number 5,888,296 [Application Number 08/956,622] was granted by the patent office on 1999-03-30 for method for making a ferroelectric semiconductor device and a layered structure.
This patent grant is currently assigned to Motorola, Inc.. Invention is credited to Jerald A. Hallmark, Daniel S. Marshall, William J. Ooms.
United States Patent |
5,888,296 |
Ooms , et al. |
March 30, 1999 |
Method for making a ferroelectric semiconductor device and a
layered structure
Abstract
A layered bismuth ferroelectric structure (12) and a method for
forming the bismuth layered ferroelectric structure (12). A
monolayer (12A) of bismuth is formed in intimate contact with a
single crystalline semiconductor material (11). A layered
ferroelectric material (12) is grown on the monolayer (12A) of
bismuth such that the monolayer (12A) of bismuth becomes a part of
the layered ferroelectric material (12). The ferroelectric material
(12) forms a layered ferroelectric material which is not a pure
perovskite, wherein the crystalline structure at the interface
between the single crystalline semiconductor material (11) and the
monolayer (12A) of bismuth are substantially the same.
Inventors: |
Ooms; William J. (Chandler,
AZ), Marshall; Daniel S. (Chandler, AZ), Hallmark; Jerald
A. (Gilbert, AZ) |
Assignee: |
Motorola, Inc. (Schaumburg,
IL)
|
Family
ID: |
24871174 |
Appl.
No.: |
08/956,622 |
Filed: |
September 29, 1997 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
714715 |
Sep 16, 1996 |
5767543 |
|
|
|
Current U.S.
Class: |
117/92;
257/E21.169; 257/E21.272; 257/E21.17; 257/E21.01; 117/103; 117/953;
117/104; 257/E29.164 |
Current CPC
Class: |
H01L
28/56 (20130101); H01L 21/2855 (20130101); H01L
29/516 (20130101); H01L 21/02197 (20130101); H01L
21/28556 (20130101); H01L 21/31691 (20130101); H01L
21/02271 (20130101); H01L 21/02269 (20130101) |
Current International
Class: |
H01L
21/316 (20060101); H01L 21/285 (20060101); H01L
21/02 (20060101); H01L 29/51 (20060101); H01L
29/40 (20060101); H01L 21/314 (20060101); C30B
023/00 () |
Field of
Search: |
;117/92,103,104,953 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
"Piezoelectric Ceramics" Bernard Jaffe, William Cook, Jr. and Hans
Jaffe, Academic Press, London and New York, 1971, pp. 213-235.
.
"Crystal Structure of Bi.sub.4 Ti.sub.3 O.sub.12 ", J. F. Dorrian,
R. E. Newnham, D. K. Smith and M. I. Kay, Ferroelectronics, Gordon
and Breach Science Publishers Ltd., Norwich, England, 1971, vol. 3,
pp. 17-27..
|
Primary Examiner: Utech; Benjamin
Assistant Examiner: Chen; Kin-Chan
Attorney, Agent or Firm: Dover; Rennie William
Parent Case Text
This is a division of application Ser. No. 08/714,715, filed Sep.
16, 1996 now U.S. Pat. No. 5,767,543.
Claims
We claim:
1. A method for fabricating a layered structure, comprising the
steps of:
providing a single crystalline semiconductor material;
forming an epitaxial metal layer on the single crystalline
semiconductor material, a metal of the epitaxial metal layer having
a solid solubility of 1.times.10.sup.19 atoms per cubic centimeter
or less, and excluding tantalum (Ta) when the single crystalline
semiconductor material is silicon; and
forming an oxide of the metal over the epitaxial metal layer.
2. A method for fabricating a layered structure, comprising the
steps of:
providing a single crystalline semiconductor material;
forming an epitaxial metal layer on the single crystalline
semiconductor material, the epitaxial metal layer including a
bismuth layered ferroelectric, and wherein a metal of the epitaxial
metal layer has a solid solubility of 1.times.10.sup.19 atoms per
cubic centimeter or less, and excludes tantalum (Ta) when the
single crystalline semiconductor material is silicon.
3. The method of claim 2, wherein the metal is selected from the
group consisting of thallium (Tl), bismuth (Bi), lead (Pb), and
tellurium (Te).
4. The method of claim 2, wherein the step of forming an epitaxial
metal layer includes using a technique selected from the group
consisting of molecular beam epitaxy (MBE), chemical beam epitaxy
(CBE), and metallo-organic chemical vapor deposition (MOCVD).
5. The method of claim 2, wherein the step of providing the single
crystalline semiconductor material includes providing single
crystal silicon as the single crystalline semiconductor
material.
6. The method of claim 2, wherein the step of forming the bismuth
layered ferroelectric includes forming the bismuth layered
ferroelectric from the group of bismuth layer ferroelectrics
consisting of bismuth titanate (Bi.sub.4 Ti.sub.3 O.sub.12),
strontium bismuth tantalate (Bi.sub.2 SrTa.sub.3 O.sub.9), and
bismuth titanium niobate (Bi.sub.3 TiNbO.sub.9).
7. A method for fabricating a layered structure, comprising the
steps of:
providing a single crystalline semiconductor material;
forming an epitaxial metal layer that includes a layer of Bi.sub.2
O.sub.2 between the single crystalline semiconductor material and a
bismuth layered ferroelectric on the single crystalline
semiconductor material, a metal of the epitaxial metal layer having
a solid solubility of 1.times.10.sup.19 atoms per cubic centimeter
or less, and excluding tantalum (Ta) when the single crystalline
semiconductor material is silicon.
8. The method of claim 7, wherein the step of forming the layer of
Bi.sub.2 O.sub.2 includes forming the bismuth layered ferroelectric
from the group of bismuth layer ferroelectrics consisting of
bismuth titanate (Bi.sub.4 Ti.sub.3 O.sub.12), strontium bismuth
tantalate (Bi.sub.2 SrTa.sub.3 O.sub.9), and bismuth titanium
niobate (Bi.sub.3 TiNbO.sub.9).
9. A method for making a ferroelectric semiconductor device,
comprising the steps of:
providing a monocrystalline semiconductor substrate;
forming an epitaxial monolayer over the monocrystalline
semiconductor substrate, wherein the epitaxial monolayer includes a
bismuth layered ferroelectric material and wherein an element of
the epitaxial monolayer has a solid solubility of 1.times.10.sup.19
atoms per cubic centimeter or less and excludes tantalum (Ta) when
the monocrystalline semiconductor substrate is silicon, wherein the
epitaxial metal layer has first and second edges;
forming an epitaxial ferroelectric layer over the epitaxial
monolayer, wherein the epitaxial ferroelectric layer has first and
second edges;
forming a gate electrode over the ferroelectric layer;
forming a first doped region adjacent the first edge of the
epitaxial ferroelectric layer; and
forming a second doped region adjacent the second edge of the
epitaxial ferroelectric layer.
10. The method of claim 9, wherein the step of forming the
epitaxial ferroelectric layer includes using a technique selected
from the group consisting of molecular beam epitaxy (MBE), chemical
beam epitaxy (CBE), and metallo-organic chemical vapor deposition
(MOCVD).
11. A method for fabricating a layered structure, comprising the
steps of:
providing a single crystalline semiconductor material;
forming an epitaxial layer on the single crystalline semiconductor
material, an element of the epitaxial layer having a solid
solubility of 1.times.10.sup.19 atoms per cubic centimeter or less
when the single crystalline semiconductor material is silicon;
and
forming an oxide of the element over the epitaxial layer.
12. The method of claim 11, wherein the element is selected from
the group consisting of thallium (Tl), lead (Pb), and tellurium
(Te).
13. The method of claim 11, wherein the step of forming an
epitaxial layer includes using a technique selected from the group
consisting of molecular beam epitaxy (MBE), chemical beam epitaxy
(CBE), and metallo-organic chemical vapor deposition (MOCVD).
14. A method for fabricating a layered structure, comprising the
steps of:
providing a single crystalline semiconductor material;
forming an epitaxial layer on the single crystalline semiconductor
material, wherein the epitaxial layer includes a bismuth layered
ferroelectric selected from the group of bismuth layered
ferroelectrics consisting of bismuth layer ferroelectrics
consisting of bismuth titanate (Bi.sub.4 Ti.sub.3 O.sub.12),
strontium bismuth tantalate (Bi.sub.2 SrTa.sub.3 O.sub.9), and
bismuth titanium niobate (Bi.sub.3 TiNbO.sub.9), and wherein an
element of the epitaxial layer has a solid solubility of
1.times.10.sup.19 atoms per cubic centimeter or less when the
single crystalline semiconductor material is silicon.
15. A method for fabricating a layered structure, comprising the
steps of:
providing a single crystalline semiconductor material;
forming an epitaxial layer on the single crystalline semiconductor
material, wherein the epitaxial layer includes a layer of Bi.sub.2
O.sub.2 between the single crystalline semiconductor material and a
bismuth layered ferroelectric, and wherein an element of the
epitaxial layer has a solid solubility of 1.times.10.sup.19 atoms
per cubic centimeter or less when the single crystalline
semiconductor material is silicon.
16. The method of claim 15, wherein the step of forming the layer
of Bi.sub.2 O.sub.2 includes forming the bismuth layered
ferroelectric from a group of bismuth layer ferroelectrics
consisting of bismuth titanate (Bi.sub.4 Ti.sub.3 O.sub.12),
strontium bismuth tantalate (Bi.sub.2 SrTa.sub.3 O.sub.9), and
bismuth titanium niobate (Bi.sub.3 TiNbO.sub.9).
Description
BACKGROUND OF THE INVENTION
The present invention relates, in general, to semiconductor
devices, and more particularly, to ferroelectric semiconductor
devices.
Ferroelectric materials have been used to form electrical
components such as capacitors, non-volatile memories, and optical
guided wave devices. Typically, these materials are deposited on a
conductive substrate which is disposed on a substrate oxide
overlying a semiconductor substrate. The substrate oxide prevents
defects that might occur at the interface between the silicon
substrate and the ferroelectric material, which defects degrade the
performance of the semiconductor device. Further, the ferroelectric
material is typically deposited as a polycrystalline film.
Accordingly, the ferroelectric material generally has poor leakage
characteristics. Moreover, the interface between a ferroelectric
material deposited directly on a semiconductor substrate and the
semiconductor substrate has generally been unsuitable for
semiconductor device applications.
Techniques for depositing the ferroelectric material include
sputter deposition using a single target, sputter co-deposition
using two or more targets, and spin-on deposition. The use of
sputtering techniques to deposit ferroelectric material directly on
a semiconductor substrate damages the semiconductor substrate,
thereby creating interface states. Spin-on deposition, on the other
hand, is performed in atmospheric conditions and results in a large
interface state density due to poor interface control. In addition,
these techniques require a high temperature anneal, e.g., about 900
degrees Celsius (.degree.C.), which adversely affects the
semiconductor substrate and thus the interface between the
ferroelectric film and the semiconductor substrate. Other drawbacks
of the spin-on deposition technique include incompatibility with
standard integrated circuit processes, precipitation of particles
in the ferroelectric materials during their deposition, and poor
adhesion of the ferroelectric material to the semiconductor
substrate.
Accordingly, it would be advantageous to have a ferroelectric
device and a method for manufacturing the ferroelectric device
wherein the ferroelectric material is lattice matched to a
semiconductor surface to minimize defects at the
ferroelectric-semiconductor interface due to strain. It would be of
further advantage to deposit a ferroelectric film having properties
that are suitable for use in a ferroelectric gate field effect
transistor. Suitable properties of the ferroelectric film include a
low interface state density, appropriate spontaneous polarization,
and an appropriate coercive field.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view of a portion of a ferroelectric
semiconductor device at an early stage of manufacture in accordance
with the present invention;
FIG. 2 is a cross-sectional view of the semiconductor device of
FIG. 1 further along in processing;
FIG. 3 is a top view of a monolayer of a metal film formed in
accordance with the present invention;
FIG. 4 is a cross-sectional view of a metal oxide film in
accordance with the present invention; and
FIG. 5 is a cross-sectional view of a ferroelectric film in
accordance with the present invention.
DETAILED DESCRIPTION OF THE DRAWINGS
Generally, the present invention provides a terminating layer on a
semiconductor that results in low stress and a low interface state
density. Furthermore, the present invention provides a
ferroelectric device and a method for manufacturing the
ferroelectric device. In accordance with the present invention, an
epitaxial layer of ferroelectric material is formed on a
semiconductor substrate using techniques such as molecular beam
epitaxy (MBE), chemical beam epitaxy (CBE), metallo-organic
chemical vapor deposition (MOCVD), or combinations thereof,
creating a layered structure. In order to achieve a low interface
state density, the growth technique must control the environment of
the substrate so that it can be made atomically clean and kept
atomically clean. Thus, the present invention provides a deposition
process in which the deposition at the surface is well controlled.
An advantage of epitaxially forming the interface layer is that the
epitaxial layer can be substantially lattice matched to the silicon
substrate and thus has a low defect density with substantially no
dislocations formed in the crystalline structure.
FIG. 1 is a cross-sectional view of a portion of a ferroelectric
semiconductor device 10 at an early stage of manufacture in
accordance with the present invention. Ferroelectric semiconductor
device 10 includes a monocrystalline semiconductor material or
substrate 11 having a major surface 13 with a ferroelectric
material 12 formed thereon. Suitable semiconductor materials for
substrate 11 include silicon, gallium arsenide, indium phosphide,
or the like. By way of example, semiconductor substrate 11 is
silicon having a <001> surface orientation. Ferroelectric
film 12 is epitaxially formed on semiconductor substrate 11 using
an ultra high vacuum deposition system such as, for example,
molecular beam epitaxy or chemical beam epitaxy, or a low pressure
metallo-organic chemical vapor deposition system.
The use of an ultra high vacuum deposition system is a means of
preventing undesired elements from destroying the electronic
properties at the interface between silicon substrate 11 and
layered ferroelectric film 12. In accordance with one aspect of the
present invention, a monocrystalline layer of ferroelectric
material is formed in intimate contact with the semiconductor
substrate. Further, the ferroelectric material has a lattice
constant substantially matching that of semiconductor substrate 11.
The method of the present invention prevents undesired material
such as, for example, an undesired oxide or contaminants from
appearing at the interface between the ferroelectric film and the
semiconductor substrate.
FIG. 2 is a cross-sectional view of ferroelectric semiconductor
device 10 further along in processing. A layer 25 of conductive
material is formed on ferroelectric film 12 (shown in FIG. 1). An
etch mask (not shown) such as, for example, photoresist, is formed
on a portion of layer 25 of conductive material. The portions of
layer 25 of conductive material and ferroelectric film 12
unprotected by the etch mask are removed by, for example, a
reactive ion etch, forming a ferroelectric gate structure 26.
Ferroelectric gate structure 26 is comprised of layer 25 and
ferroelectric gate dielectric 22 which is the remaining portion of
ferroelectric material 12. Thus, the remaining portion of layer 25
serves as a gate electrode. The remaining portions of the layer of
photoresist are removed.
An impurity material of N conductivity type such as, for example,
phosphorus is implanted into the portions of silicon substrate 11
adjacent to ferroelectric gate dielectric 22 to form doped regions
23 and 24. Doped regions 23 and 24 serve as source and drain
regions, respectively, of ferroelectric semiconductor device 10.
Techniques for applying and removing photoresist, etching a
ferroelectric film, and implanting an impurity material are well
known to those skilled in the art. Although not shown, gate
contacts, source contacts, and drain contacts may be formed to
contact gate electrode 26, source region 23, and drain region 24,
respectively. It should be noted the present invention is suitable
for forming N and P channel enhancement mode field effect
transistors and N and P channel depletion mode field effect
transistors. Thus, the source/drain regions can be formed using an
impurity material of P conductivity type such as, for example,
boron.
FIG. 3 illustrates a top view of a monolayer 12A of a metal element
in accordance with the present invention. Monolayer 12A is also
referred to as a precursor layer, an initial layer, or an interface
layer. It should be noted that the letter "A" has been appended to
the reference number 12 to illustrate that layer 12A is one layer
of layered ferroelectric film 12 shown in FIG. 1. Because FIG. 3 is
a top view of a crystalline structure, layers of silicon below
monolayer 12A are also shown. It should be further noted that the
same reference numbers are used in the figures to denote the same
elements. Monolayer 12A is an epitaxial metal layer comprised of a
monolayer of a metal element, excluding tantalum (Ta) when
substrate 11 is silicon, having a maximum solid solubility limit of
less than or equal to 1.times.10.sup.19 atoms per cubic centimeter
(atoms/cm.sup.3). Examples of suitable elements for monolayer 12A
on silicon include bismuth (Bi), tellurium (Te), lead (Pb),
thallium (Tl), or combinations thereof. Bismuth, for example has a
solid solubility of approximately 1.times.10.sup.18 atoms/cm.sup.3
in silicon.
A key feature of these elements is that they fill dangling bonds
extending from the monocrystalline lattice of the semiconductor
material, e.g., dangling bonds extending from silicon. A low solid
solubility is important because these materials do not react
strongly with the bulk of the semiconductor material. Forming
layers that react strongly with the bulk of the semiconductor
material can result in the uncontrolled formation of unwanted
compounds, e.g., metal silicides for a silicon-metal system. By
using materials with a limited solid solubility, metal layers can
be deposited without making unwanted compounds. Also, single
monolayers of these metals can be deposited in a self-limiting
fashion. In other words, more than a monolayer may be deposited
with the excess not being able to stick to the surface within
specified processing conditions such as, for example, a specified
temperature range. The self-limiting aspect of the present
invention provides a manufacturable interface. Accordingly, a
monolayer 12A of bismuth is an initial layer which is part of a
layered ferroelectric material described with reference to FIG.
4.
FIG. 4 is cross-sectional view of another precursor layer 12B
formed on a single crystal silicon substrate in accordance with the
present invention. It should be noted that the letter "B" has been
appended to reference number 12 to illustrate that layer 12B is one
portion of the embodiment of layered ferroelectric film 12 shown in
FIG. 1. It should be further noted that precursor layer 12B can be
viewed as a single layer formed on monolayer 12A or, alternatively,
it can be viewed as a single layer that includes monolayer 12A.
Precursor layer 12B is cubic Bi.sub.2 O.sub.2 which is epitaxially
grown on silicon substrate 11. Cubic Bi.sub.2 O.sub.2 is also
referred to as cubic BiO because they are stoichiometrically
equivalent. Thus, cubic Bi.sub.2 O.sub.2 is in intimate contact
with the single crystal material of substrate 11. It should be
understood that cubic Bi.sub.2 O.sub.2 is different from bismuth
oxide (Bi.sub.2 O.sub.3) because it is not a stable compound in
bulk form. In other words, cubic Bi.sub.2 O.sub.2 forms a
metastable layer that ceases to grow beyond a finite thickness.
Typically, the number of layers of cubic Bi.sub.2 O.sub.2 in cubic
Bi.sub.2 O.sub.2 layer 12B ranges from one to three. Another
difference between bismuth oxide (Bi.sub.2 O.sub.3) and Bi.sub.2
O.sub.2 is that bismuth oxide (Bi.sub.2 O.sub.3) is a hexagonal
structure whereas Bi.sub.2 O.sub.2 is a cubic structure.
FIG. 5 is a cross-sectional view of a layered epitaxial
ferroelectric film 12C formed on cubic Bi.sub.2 O.sub.2 layer 12B
in accordance with the present invention. It should be noted that
the letter "C" has been appended to the reference number 12 to
illustrate that layer 12C is another portion of the embodiment of
layered ferroelectric film 12 shown in FIG. 1. It should be further
noted that the same reference numbers are used in the figures to
denote the same elements. By way of example, ferroelectric layer
12C is a layered Bi.sub.4 Ti.sub.3 O.sub.12 structure.
In accordance with the present embodiment, the combination of
layers of cubic Bi.sub.2 O.sub.2 and Bi.sub.2 Ti.sub.3 O.sub.10
form bismuth titanate (Bi.sub.4 Ti.sub.3 O.sub.12). The average
lattice constant of this material is 0.5430 nanometers (nm) which
is essentially the same as the lattice constant of crystalline
silicon, i.e., 0.543095 nm. A unit cell of bismuth (Bi.sub.4
Ti.sub.3 O.sub.12) is stoichiometrically completed when the
Bi.sub.2 Ti.sub.3 O.sub.10 is deposited on the cubic Bi.sub.2
O.sub.2.
Although one embodiment of the present invention has been described
as showing a layer of bismuth titanate formed on the semiconductor
substrate, this is not a limitation of the present invention. Other
suitable ferroelectric films include bismuth layered ferroelectrics
such as, for example, strontium bismuth tantalate (Bi.sub.2
SrTa.sub.3 O.sub.9), and bismuth titanium niobate (Bi.sub.3
TiNbO.sub.9).
By now it should be appreciated that a ferroelectric film having a
layered bismuth ferroelectric structure and a semiconductor device
that includes the layered ferroelectric structure have been
provided. The ferroelectric film is a layered epitaxial film that
is formed using an ultra high vacuum deposition system such as
molecular beam epitaxy or chemical beam epitaxy or a low pressure
metallo-organic chemical vapor deposition system. Formation of
ferroelectric epitaxial films in accordance with the present
invention decreases the number of interface states and provides
lattice matching between a semiconductor layer and the
ferroelectric film. Further, the epitaxial layer of ferroelectric
material has an atomic spacing which is commensurate with the
monocrystalline semiconductor substrate. One may also deposit or
grow a film with a somewhat larger or smaller lattice constant than
that of the substrate on which the film is grown. The lattice
constant of the film can be forced to be commensurate with that of
the substrate while under strained conditions by keeping the grown
film less than the critical thickness. Other features of the
present invention are that it provides a ferroelectric film and
method for fabricating the layered ferroelectric film without a
pure perovskite structure, and the present invention provides a low
interface state density, appropriate spontaneous polarization, and
an appropriate coercive field.
While specific embodiments of the invention have been shown and
described, further modifications and improvements will occur to
those skilled in the art. It is understood that this invention is
not limited to the particular forms shown and it is intended for
the appended claims to cover all modifications of the invention
which fall within the true spirit and scope of the invention. For
example, FIGS. 3-5 illustrate the assumed positions of the bismuth
atoms relative to the silicon surface atoms. Present analytical
techniques do not allow precise determination of the exact position
of the atoms. Thus, FIGS. 3-5 provide an illustration of the
present invention; however, deviations from the assumed atomic
positions do not detract from spirit and scope of the
invention.
* * * * *